CN104321910A

CN104321910A - Improved lead-acid battery construction

Info

Publication number: CN104321910A
Application number: CN201380023455.9A
Authority: CN
Inventors: S·克里斯蒂; Y·S·王; G·泰特曼; J·巴拉哈姆森
Original assignee: Canterprise Ltd
Current assignee: Canterprise Ltd; Arcactive Ltd
Priority date: 2012-03-08
Filing date: 2013-03-08
Publication date: 2015-01-28
Anticipated expiration: 2033-03-08
Also published as: US10903501B2; KR102046199B1; CN107644978B; EP3367482A1; EP2820702A2; MX2014010616A; ES2682764T3; RU2014140598A; ES2777475T3; BR112014022226B1; RU2638532C2; CA2866368A1; KR20150022750A; CN104321910B; JP6509562B2; CN107644978A; CA2866368C; WO2013133724A9; ZA201407261B; US9543589B2

Abstract

Batteries comprise a carbon fibre electrode construction of the invention and have improved DCA and/or CCA, and/or may maintain DCA with an increasing number of charge-discharge cycles, and thus may be particularly suitable for use in hybrid vehicles.

Description

The lead-acid battery structure improved

Technical field

The present invention relates to the battery structure of the improvement of plumbous acid battery, specifically but not exclusively relate to the automobile batteries of hybrid vehicle.

Background technology

Lead-acid battery is stored by the electrochemical reaction on its electrode surface and releases energy.Each battery being in fully charged state is included in dilute sulfuric acid (H ₂sO ₄) electrolyte in Element Lead (Pb) and brown lead oxide (IV) (PbO ₂) electrode.In discharge condition, two kinds of electrodes all become lead sulfate (II) (PbSO ₄), electrolyte is lost its sulfuric acid dissolved and is mainly become water.In grid type plate structure, each pole plate comprises at first with the lead grid lattice that the paste of the mixture comprising leaded oxide (Pb and PbO) and dilute sulfuric acid is filled.This structure is (the first charging and discharging cycle in battery (cell) forming process, in this process, produce between adjacent particles and connect (linkage)) allow the acid in paste and the lead oxides in pole plate to react, increase conductivity and effective surface area, so, battery capacity is increased.Paste also can comprise carbon black, blanc fixe (fine barium sulfate) and lignosulfonate.

The demand to automobile batteries (modal is lead-acid battery) is increased by the automobile power hybridization of the requirement drive of the worldwide increasing fuel economy to lower motor vehicle emission and/or increase.Such as, European Union is that new cars establish the long-term emissions object reaching before the year two thousand twenty and be no more than 95g carbon dioxide/km.

Many automobiles being power with new internal combustion engine (gasoline, diesel engine or combustion gas) also have idling elimination function---close when engine is configured to when vehicle stationary or travels with low velocity.Such automobile is called as stopping-startup automobile or micro hybrid vehicle.Each engine restart all absorbs energy from battery, if this specific energy occurs faster by recharging to replace, only in the time period of relatively short engine running, such as, in incommutation, so battery electric quantity (or state of charge) can not be kept.In the time period that vehicle motor is closed also from battery Absorption Current, to keep other functions in automobile, such as air-conditioning, broadcast receiver etc. (being called as " hotel load ").Battery electric quantity may decline be enough to make Vehicular battery management system then will refuse idling elimination function to prevent any further engine stop-startup, until the recovering state of the electricity of battery.So, in order to even such as keep battery electric quantity in busy incommutation, the battery for such stopping-startup or micro hybrid vehicle should have high dynamically charging by (DCA) rate, and this refers to that battery will accept the speed of charging.

Have the automobile of the hybrid power of higher level, comprise the automobile with explosive motor and motor, generally include regenerative braking, wherein, brake weight is applied by generator, carrys out the power storage of self generator in Vehicular battery.During the explosive motor out-of-operation period driving generator (comprising alternating current generator here), Vehicular battery is only by the current charges from regenerative braking.Under regenerative braking, relatively high charging current is provided to Vehicular battery in the short time, and therefore, the battery with the hybrid vehicle of regenerative braking also should have high DCA.Complete motor vehicle also comprises regenerative braking.

The charging system of hybrid vehicle is configured to use engine-driven generator, charge completely so that the charged state of Vehicular battery is remained on to be less than, such as, such as, about 80% charging, can be used for accepting the capacity from the extra rechargeable energy of regenerative braking generally to have.But; As time goes on battery DCA usually can be; along with increasing of electric discharge and the number of times in charging (be less than completely charge) cycle, and decline, AGM battery usually within several thousand cycles in about 0.1 to 0.3A/Ah (or 0.1 to 0.3C) operation.The loss of this charge acceptance reduces the fuel oil saving ability of automobile; Auto-maker wishes that battery can accept up to 2A/ah within the time period of 5 to 10 seconds ideally, or even 3A/Ah, saves potentiality with the fuel oil maximizing start/stop and regenerative braking capability.But any improvement higher than 0.1 to 0.3A/Ah is all valuable improvement.Usually, the charging system of hybrid vehicle is configured to allow battery discharge and then (use engine-driven generator) to charge the battery.Generally speaking, automobile batteries management system will charge (or " reduction " battery), to recover battery DCA, such as every three months periodically to battery completely.Desirable lead-acid battery, especially for the lead-acid battery of hybrid vehicle, by maintenance DCA without the need to periodically charging completely, or keeps higher DCA to lead to major general between reduction cycle.

In lead-acid battery, DCA determines primarily of the charging reaction in negative electrode.

Battery also should meet other requirements, such as has high volume energy density.Volume energy density (VED) refers to the energy that the per unit volume of electrode provides.The Acid Battery System closed also should have low water consumption.Particularly, Vehicular battery should be able to be provided for the high electric current of generator starting when low temperature.Cold start amperage (CCA) test can the ability of test battery this respect.

U.S. Patent No. 7569514 describes and utilizes activated carbon as the electrode in absorption type glass fibre cotton battery, to overcome sulphation, to improve the dynamic charge acceptance of battery thus.

U.S. Patent No. 4429442 describes a kind of lead-acid battery electrode plate, comprises metal grate and active material (active mass), and comprises one deck carbon fibre material in the side of active material, with the mechanical integrity of enhanced activity material.

U.S. Patent No. 4342343 describes the negative polar plate of lead acid storage battery with the carbon fiber of interconnection on the face being coated with cream pole plate.In the fabrication process, then it is pressed on pole plate strengthens formability by fiber being fixed to paper carrier.

U.S. Patent No. 6617071 describes the electrode with the conductive polymer matrix formed on the surface of screen, and wherein, conductive polymer matrix comprises the ultra-fine of active material or nanometer particle.

Our International Patent Application Publication WO2011/078707 discloses a kind of lead-acid battery, comprise conductive fiber material silk as collector, with low inter-fiber spaces and the conductive chain of the particle based on lead being attached to fiber, provide the battery performance of improvement, particularly DCA.

Summary of the invention

Electrode that is that the target of at least some embodiment of the present invention is to provide improvement or that at least can select else and/or battery unit and/or battery, this electrode and/or battery unit and/or battery are especially but be not necessarily applicable to hybrid vehicle and/or the method for the manufacture of hybrid vehicle exclusively.

Broadly say, on the one hand, the present invention includes a kind of lead-acid battery or battery unit, it comprises at least one (non-synthetic or synthesis) electrode, this electrode comprises conductive fiber material as collector, conductive fiber material comprises the voidage (being the volume ratio that the hole between lead and conductive fiber occupies) when being full of electricity at least about 0.3, and the lead (in any form) when being converted to volume ratio in the scope of about 0.7:1 or about 1:1 to about 15:1 or about 10:1 is loaded into than (respectively all at least one major part of electrode with the quality of conductive fiber quality, more preferably, substantially all on electrode).

Broadly say, on the other hand, the present invention includes a kind of method for the manufacture of lead-acid battery or battery unit, the method comprises: form at least one (non-synthetic or synthesis) electrode, it comprises conductive fiber material as collector, conductive fiber material comprises, when being full of electricity, voidage (being the volume ratio that the hole between lead and conductive fiber occupies) at least about 0.3, and when being converted to volume ratio, the lead in the scope of about 0.7:1 or about 1:1 to about 15:1 or about 10:1 and the quality of conductive fiber quality are loaded into ratio.

In certain embodiments, voidage about 0.3 with about between 0.9, about 0.3 and about between 0.85, more preferably, about 0.3 with about between 0.8, more preferably, about 0.5 with about between 0.98, further preferably, about 0.8 with about between 0.95.

In certain embodiments, when being converted to Pb, the volume of active material and conductive fiber is loaded into ratio at about 0.7:1 or about 1:1 with about between 7:1, or at about 1.5:1 with about between 5:1, or at about 2:1 with about between 4:1.

Usually, voidage can exist as the passage formed between lead and carbon, to make to form lead button between each carbon fiber.In certain embodiments, the equispaced between conductive fiber between about 0.5 and about 10 fibre diameter, more preferably, between about 1 and about 5 fibre diameter.In certain embodiments, between the average fiber between fiber, interval is less than 50 microns or be less than 20 microns.Preferably, be interposed between at least major part of material between described average fiber, more preferably, on all material substantially.In a preferred embodiment, fiber diameter is less than about 20 microns or be less than about 10 microns.

Broadly say, on the other hand, the present invention includes a kind of lead-acid battery or battery unit, it comprises at least one (non-synthetic or synthesis) electrode, this electrode comprises conductive fiber material as collector, conductive fiber material comprises the voidage (being the volume ratio that the hole between lead and conductive fiber occupies) when being full of electricity at least about 0.3, and the loading of the plumbous volume of (in any form) and the volume of conductive fiber is than (respectively all at least major part of electrode), they define a point jointly in voidage (x-axis) and the volume of lead and the chart of the loading of the volume of conductive fiber than (y-axis), in the region that another line that the x-axis space angle value that slope on the line that the x-axis space angle value that it is approximately-1/0.02 that this point drops on by the slope on described figure is about 98% and described figure is about-1/0.3 is about 70% defines.

In certain embodiments, voidage and when being converted to volume ratio plumbous loading with the weight of the quality of conductive fiber than jointly on described chart, define a point, this point drop on slope be approximately-1/0.03 the x-axis space angle value line that is about 97% and the region that limits of the slope x-axis space angle value that is about-1/0.2 another line that is about 80% in, or drop on slope be approximately-1/0.04 the x-axis space angle value line that is 96% and the region that defines of the slope x-axis space angle value that is about-1/0.15 another line that is 85% in.

Broadly say, on the other hand, the present invention includes a kind of lead-acid battery or battery unit, comprise at least one (non-synthetic or synthesis) electrode, this electrode comprises carbon fibre material as collector, and carbon fibre material has the carbon fiber volume ratio being less than 40%, and the volume of lead (in any form) being greater than 0.5 with the loading of the volume of carbon fiber than (respectively all at least major part of electrode, more preferably, substantially all on electrode).

In certain embodiments, carbon fiber volume ratio is less than 30%, and the quality of the lead and carbon fiber that are converted to volume ratio is loaded into than being greater than 0.7, or carbon fiber volume ratio is less than 20%, and the quality of the lead and carbon fiber that are converted to volume ratio is loaded into than being greater than 1:1.

Broadly say, on the other hand, the present invention includes a kind of lead-acid battery or battery unit, it comprises at least one (synthesis) electrode, this electrode comprises conductive fiber material as collector, and comprising metal grate, it at least 20% is the catalytic activity material of the generation electric current of conductive fiber material that electrode also comprises it.

In certain embodiments, at least 40%, 50%, 80% or be no more than 80% active material in conductive fiber material.So, the active material being less than 80%, 60%, 50% or 20% can be dispersed in metal grate.

In certain embodiments, conductive fiber material comprises carbon fibre material, and metal grate comprises lead grid lattice.

In certain embodiments, conductive fiber material is as multiple layers of existence, and at least one layer is on the either side of metal grate.Can alternatively, conductive fiber material exists as the individual layer on the side of metal grate.

Metal grate can have the shallow surface area similar with conductive fiber material element, or similar height and width dimensions, specifically in primary flat, but, in alternative embodiment, metal grate can have reduced size, such as, less height and width dimensions, and such as can comprise narrower leads band between the larger carbon fiber layer of on either side thereof two.

Carbon fiber layer is connected to metal grate conductively, to make grid from carbon fiber layer received current, and from its external connecting electrode.

Conductive fiber material can be textile material (comprising the graticule fiber of intersection), braided material or non-woven material, such as felt-like material.One or more positive electrode, one or more negative electrode or both, can be made up of the conductive fiber material of one or more layers.Preferably, the density of conductive fiber material density ratio lead is light.Current collector material can comprise carbon fibre material, such as weaving or braided material or felted or nonwoven carbon fibre fabric.Can heat-treat carbon fiber current collector material, to reach enough temperature, to improve its conductivity.Heat treatment can pass through arc discharge.Usually, conductive fiber material has length and width dimensions in the primary flat of material, and the degree of depth of described primary flat perpendicular to material.Collector fiber material can have at least 0.2mm or at least 1mm and/or be less than the mean depth of material of 5mm or 3mm or 2mm.Collector can comprise multilayer conductive fiber material.Current collector material has and is less than 10 Ω mm, preferably, is less than the volume resistivity of 1 Ω mm or 0.1 Ω mm.

Broadly say, on the other hand, the present invention includes a kind of lead-acid battery or battery unit, comprise at least one electrode, at least one electrode described comprises conductive fiber material as collector, and comprising metal grate, electrode also comprises electric current and generates catalytic activity material, and conductive fiber material has the volume resistivity being less than 10 Ω mm.

In at least some embodiments, comprise that the battery unit of electrode structure of the present invention and/or battery can have improvement or higher DCA and CCA, and/or the charge-discharge cycle quantity of increase can be utilized to lead to keep the DCA of DCA or higher, so, hybrid vehicle can be specially adapted to.That identical embodiment of the present invention or other embodiment battery units and/or battery also or alternatively can have the water consumption of reduction and/or a raising or higher VED and/or raising battery life.

Term as used in this description " comprises " expression and " comprises at least in part ".Comprising each narrative tense that term " comprises " when explaining in this specification, also can exist divided by the feature beyond the feature that this term starts.The relevant term such as " to comprise " and so on will be explained in the same way.

Accompanying drawing explanation

The present invention is further described with reference to accompanying drawing exemplarily, wherein:

Fig. 1 is the chart that the active material of various negative electrodes (all be all made up of the active material being loaded in carbon base body) that uses in lead-acid battery cells and the ratio (volume ratio) of carbon contrast voidage,

Fig. 2 is the chart that the ratio (volume ratio) of active material and carbon contrasts the region of voidage, also comprises the various electrodes in Fig. 1,

Fig. 3 a schematically illustrates carbon fiber electrode, with the metal claw connecting the electrode formed on carbon fibre material by compression casting for outside, Fig. 3 b shows difform pawl, with tongue piece, and Fig. 3 c shows the cross section of the multilayer carbon fibre material with pawl

Fig. 4 schematically illustrates the electrode of embodiments of the invention from side, with the metal line or belt being attached to side as grand yardstick collector,

Fig. 5 is the schematic cross-section of the electrode of embodiments of the invention, with the metal line or belt being adhered to side as grand yardstick collector,

The schematic cross-section of the electrode that Fig. 6 is made up of two sections of the electrode material of embodiments of the invention, with the metal line or belt embedding as grand yardstick collector or add in-between,

Fig. 7 shows the schematic cross-sectional view of the felted thing for dividing the carbon fiber electrode material forming some embodiments of the present invention,

Fig. 8 schematically illustrates a kind of form of reactor, for continuously or semi-continuously activating the carbon fibre material be used as according to current collector material of the present invention,

Fig. 9 is the detailed schematic views of the material path between the electrode of Fig. 8 and the electrode of reactor,

Figure 10 shows the DCA testing algorithm mentioned in experimental work subsequently describes,

Figure 11 shows the two-forty DCA performance of two the composite electrode N359 and 371 mentioned in experimental work subsequently describes,

Figure 12 shows the CCA performance of the electrode N349 mentioned in experimental work subsequently describes, and this uses SAE J537 to test with the two-forty of the 310mA/ square centimeter of the electrode surface area in the face of another electrode,

Figure 13 shows current vs charging overpotential (Tafel Line) of the electrode 411 mentioned in experimental work subsequently describes, and compared with traditional electrode, demonstrates similar water consumption attribute,

Figure 14 shows current vs charging overpotential (Tafel Line) of the electrode 305 mentioned in experimental work subsequently describes, and shows the attribute that need water consumption more less than traditional electrode,

Figure 15 shows the two-forty DCA performance of the electrode 409 (with the electrode that the 60mm of sets of lines fluid is long) mentioned in experimental work subsequently describes, and demonstrates DCA performance well compared with traditional electrode,

Figure 16 shows the two-forty DCA performance of the electrode 365 (60mm is long, does not have sets of lines fluid) mentioned in experimental work subsequently describes, and it has the electrode but still DCA performance more better than traditional electrode that are less than with sets of lines fluid,

Figure 17 shows the two-forty DCA performance of the electrode 356 mentioned in experimental work subsequently describes, initial 35, after 000 cycle (as shown in figure 16), length reduction is to 30mm, then testing with the density of charging current identical above, and show outstanding DCA performance, and

Figure 18 shows compared with the typical DCA of traditional lead acid accumulator, when using Axion DCA test, and the DCA performance of electrode 410.

Embodiment

With reference to figure 1, this figure is the chart that the ratio (volume ratio) of active material and carbon contrasts voidage, in one embodiment, at least one electrode is comprised according to lead-acid battery of the present invention or battery unit, it comprises conductive fiber material as collector, conductive fiber material comprises the voidage (being the volume ratio that the hole between lead and conductive fiber occupies) when being full of electricity at least about 0.3, and the lead (in any form) when being converted to volume ratio in the scope of about 0.7:1 or about 1:1 to about 15:1 or about 10:1 is loaded into than (supposing that all active materials are converted to Pb all completely when being full of electricity) with the quality of conductive fiber quality.In certain embodiments, voidage is about between 0.3 and 0.9, about 0.3 with about between 0.85, about 0.3 with about between 0.80, about 0.5 with about between 0.98, about between 0.7 and 0.95, about between 0.5 and 0.98, or about 0.8 with about between 0.95, when being converted to Pb, the volume of active material and conductive fiber is loaded into ratio at about 0.7:1 or about 1:1 with about between 7:1, at about 1.5:1 with about between 5:1, or at about 2:1 with about between 3:1.

The ratio of active material volume and carbon volume refers to the volume containing the active material of Pb in conductive fiber matrix.Voidage refers to that voidage between the particle of active material and conductive fiber matrix is divided by cumulative volume.Figure 1 illustrates the ratio of the solid volume for the many Different electrodes contrast voidage described in test examples subsequently.Fig. 1 allows different matrix voidages, utilizes solid active material to fill the change (such as, when being coated with cream) of the degree of this matrix voidage, and the change of charged state.Between the volume ratio that every bar line is plotted in two kinds of extreme form of the active material comprised in given carbon base body and voidage.Circulate for most of electrochemistry, these two kinds of forms are Pb and PbSO ₄.The electrode utilizing specific carbon base body to make occupies the single line on chart, and through there is no the point of matrix voidage of active material.The degree (and it is in the form of such as PbSO4 or Pb) that active material is loaded into determines electrode (current) by which point on (directly) line is represented, consider multi-form different densities, and each exists how many.Such as, if first matrix is loaded into PbSO4, be then full of electricity to Pb, this formation is represented by the movement along one section of line, from " discharging completely " to " being full of electricity ".If first matrix is loaded into PbO, be then full of electricity to be converted into Pb, so, draw a different line to represent the path from PbO to Pb.But after this is transformed into Pb first, Pb and PbSO will be followed in the path of following any circulation subsequently ₄between line.So, from then on completely the charged/discharged of charge point will by along being first loaded into PbSO ₄time the path of same line represent.Only when being full of electricity, (that is, at 100%Pb) uses PbO as the electrode of precursor just at more useful PbSO ₄/ Pb line represents, after this, that is, in further cyclic process, electrode path will on this line.In FIG, be labeled as the line of 349,363 and 441 for electrode, its structure describes in experimental example subsequently.Each line under point all represent that the active material of all loadings has been converted into the situation of Pb all.

Voidage in the electrode of lead-acid battery cells or battery is for comprising wherein a kind of active material---acid and for permission ion close to provide or connect nucleophobic surface be important.This volume is expressed as the ratio (" voidage ") that the part comprising electrolytical electrode accounts for cumulative volume by us.Plumbous volume refers to the material (Pb) that can produce electric charge potentially or accept it with the ratio of the volume of the conductive fiber of such as carbon fiber and so on, and provide the balance between the conductive fiber material of such as carbon fiber and so on of passage the catalytic surface of electrochemical reaction (alternatively, be also) for electronics.This ratio can be expressed as volume ratio.(PbSO can be only had for fully charged state (only having Pb to exist) and complete discharge condition ₄) calculate volume ratio and mass ratio.In ordinary cycle charging and discharging, discharge at PbSO ₄complete before 100% reaction.Any fixed electrode of giving can be characterized by two parameters: be 1. loaded into the matrix voidage before active material (or more easily, matrix material divides rate, 1 deduct this voidage), and, the 2. volume ratio of active material and carbon base body when active material is converted completely into lead.Further parameter can represent on chart.The utilance of the lead of electric charge is provided to be that electrode can from Pb to PbSO in discharge process ₄point rate in total possible path of experience.

For the voidage that the volume ratio that reaction rate is important is electrode material and leaded particle.This voidage is needed to spread to reaction surface with from reaction surface to allow the ion diffuse of acid and Pb++.

Fig. 2 is similar to Fig. 1, but also show the line characterized by some carbon base body volume fraction, and the ratio (volume ratio) that defining active material and carbon contrasts the region of voidage.The line a1 being labeled as C=2% extends with the x-axis space angle value of slope-1/0.02 from 98%, and the line a2 being labeled as C=30% extends with the x-axis space angle value of slope-1/0.3 from 70%.The electrode of various embodiments of the present invention is, when being full of electricity, its voidage and quality that is plumbous and conductive fiber quality are loaded into the electrode of a point in the region defining between line a1 and a2 than (when being converted to volume ratio).

The line b1 being labeled as C=3% extends with the x-axis space angle value of slope-1/0.03 from 97%, and the line b2 being labeled as C=20% extends with the x-axis space angle value of slope-1/0.2 from 80%.The electrode of the preferred embodiments of the present invention is, when being full of electricity, its voidage and quality that is plumbous and conductive fiber quality are loaded into the electrode of a point in the region defining between line a1 and a2 than (when being converted to volume ratio).

The line c1 being labeled as C=4% extends with the x-axis space angle value of slope-1/0.04 from 96%, and the line c2 being labeled as C=15% extends with the x-axis space angle value of slope-1/0.15 from 85%.When being full of electricity, its voidage and quality that is plumbous and conductive fiber quality are loaded into the electrode of a point in the region defining between line a1 and a2 than (when being converted to volume ratio), are the electrodes of preferred embodiment of the present invention.Specifically, such electrode may be used for being formed battery unit or the battery of that have raising or higher DCA and CCA, and can have low water consumption, is specially adapted to hybrid vehicle.

Line a1 and a2, b1 and b2 is described with the formula of the ratio of the quality of conductive fiber by the quality relating to voidage and lead, and the slope of c1 and c2:

R = \frac{1 - φ_{c}}{φ_{c}} - \frac{ϵ}{φ_{c}}

Wherein, ε is voidage, and R is plumbous quality and the ratio of the quality of conductive fiber, φ _cit is the volume fraction of carbon base body.Minimum point on this line is the point describing completely plumbous situation, can be labeled as R _pb, ε _pb.

Cycle performance can depend on keep Pb and PbSO after many circulations ₄the suitably little particle size of particle.This little particle size provides PbSO ₄or Pb is fully dissolved into enough surface areas of Pb++, with when particle is close to carbon fiber surface, provide required speed and electric current, this can produce reaction by catalytic current.After many circulations particle size can and conductive fiber between the size tight association of inter-fiber spaces so that particle is applicable to being present between them.So, the diameter of the conductive fiber under same total volume fiber divides rate is less, and the gap between it will be less pro rata, and active particle also will be less pro rata.Less fiber can be utilized to realize high surfaces area and higher rate.

Relative to the ratio of particle size with the diameter of conductive fiber, along with in electrode cycle process, particle size is in wide variation, and last particle size has nothing to do with initial size to a certain extent.Such as, but initial size should be selected enough little, to put between the fibers like a cork, such as, for 7 or 8 lim diameter fibre, be less than about 10 microns.It is expected to, in charging process, each carbon fiber is to the PbSO of surrounding ₄the ablation action of particle, makes these particles be difficult to become large in many cycle periods.So, can reduce or avoid " sulphation ", and obtain long cycle life.

As previously mentioned, conductive fiber material can be textile material (comprising the graticule fiber of intersection), the material of braiding, or non-woven material, such as felt-like material.Current collector material preferably has and is less than 10 Ω mm, preferably, is less than the volume resistivity of 1 Ω mm or 0.1 Ω mm.Material can comprise carbon fibre material, that such as weave or braiding or carbon fibre fabric that is non-woven or felted.More favourable compared with the textile material in the regular crosspoint with graticule fiber at a right angle with the non-woven material in crosspoint with random fibre matting point.

Suitable carbon fibre material can comprise artificial silk, polyacrylonitrile, phenolic resins, or resin material, or obtains from above-mentioned material.

Usually, conductive fiber material has the average thickness of length and width dimensions and the described primary flat perpendicular to material at the primary flat of material, and it can such as about 0.2mm or about 1mm and/or be less than 5mm or be less than 3mm or be less than 2mm.

In at least some embodiments, conductive fiber material also has at about 0.5 to about 10 times, or about 1 and about 5 times to average fibre diameter, or is less than about 20 microns, or the equispaced between the conductive fiber being less than in the scope of about 10 microns, and be less than the average conductive fiber diameter of about 10 microns.

By splitting thicker material in face, the low-down felted of thickness or other non-thermoplastic plane electrode materials can be produced, such as, such as, the thickness of 2.5mm or less.That is, material one or many can be cut at its in-plane, thicker non-woven material to be divided into multiple with similar length and width, and thickness be narrowed down to starting sheet.This schematically illustrates in figure 6, the figure shows fine cut blade 60, and this blade 60 passes through continuously around, and driven by driving roller 61 and 62, carbon felt 63 is planar cut into slices by lathe 64, and to form equal length and width, but thickness only has two carbon felts of half.Can planar split each carbon plate produced further.

The carbon fibre material of weaving can be made into by carbon fibre tow, carbon fibre tow is pulled off, namely, after the fabrication, stretch the tow of a large amount of continuous carbon fibre silks, so that single continuous fibers are broken into shorter silk, and when each is broken the end of longitudinal separating wire, this has the effect of the silk number reducing carbon fibre tow.The tow (as rope) of the reduction silk number that distortion produces, to keep strand integrity.Such as, can 50 be broken, the tow of 000 continuous fibers, to produce the much longer tow be made up of 600 shorter monofilament, then, such as, distortion tow.

In at least some embodiments, conductive fiber material comprises the silk of average length in 3 scopes to 50mm.

One or more negative electrodes of battery unit or battery can be formed as described above, one or more positive electrode, or both.

In a preferred embodiment, the natural conduction of conduction current-collecting member fiber.In a preferred embodiment, electrode fiber is carbon fiber.But, in certain embodiments, carbon fibre material is processed, to improve conductivity.In other embodiments, electrode fiber can be the minute yardstick material not too conducted electricity, and its fiber conduction or the coating of more conducting electricity cover.In certain embodiments, the fiber of current collector material can scribble Pb or the material based on Pb.Such as, one or more negative electrode can scribble Pb, and positive electrode scribbles Pb, then, scribbles PbO thereon ₂.

Preferably, current collector material and its fiber are soft, this will contribute to the change adapting to be attached to the volume of the active material of current collector material in circulating battery process, minute yardstick fiber also can reinforce active material, and this two attribute all contributes to come off (the sloughing off) of the active material reducing the electrode in using.

In certain embodiments, conductive fiber material comprises the independent collector of or each electrode.

Can alternatively, except the conductive fiber material of carbon fiber, one or each electrode can comprise also as the metal grate of collector.In a preferred embodiment, conductive fiber material comprises carbon fibre material, and metal grate comprises lead grid lattice.One or more carbon fiber layer is connected to metal grate conductively, so that grid is from carbon fiber layer received current, and from its external connecting electrode.

The negative pole of each battery unit or positive pole or both can comprise metal grate.

When electrode comprises metal grate, preferably, the electrolyte active principle of generation electric current of at least 20% is dispersed in conductive fiber material.In a preferred embodiment, at least 40%, 50%, 80% or active principle more than 80% be dispersed in conductive fiber material.So, the active principle being less than 80%, 60%, 50% or 20% can be dispersed in (particularly, in its aperture) in metal grate.

In certain embodiments, at least 20% but the active principle being no more than 40% be dispersed in conductive fiber material.

In a preferred embodiment, conductive fiber material exists as multilayer, and one or more layer is on the either side of metal grate.Can alternatively, conductive fiber material is present on the side of metal grate as individual layer.

Metal grate can have the shallow surface area similar with conductive fiber material element, or similar height and width dimensions, particularly in primary flat, but, in an alternate embodiment, metal grate can have reduced size, such as, less height and width dimensions, and can comprise on either side thereof, such as, the narrower leads band between two larger carbon fiber layers.

Usually, in battery or battery unit manufacture process, inject minute yardstick current collector material under stress together with paste, the preferred form of paste comprises the PbO particle of Pb and Pb and the mixture of PbO and dilute sulfuric acid.Can alternatively, paste can comprise lead sulfate (PbSO ₄) particle and dilute sulfuric acid.In certain embodiments, the paste be injected in electrode comprises dilute sulfuric acid, and dilute sulfuric acid presses the weighing scale of sulfuric acid paste, is being greater than 0% and about between 5%, or 0.25% with about between 3%, or 0% with about between 2%, or between 0.5% and 2.5%.Particle based on Pb can comprise particle that is that grind or that chemically formed, and this particle can have 10 microns or less mean size, enough little of in the interval entered like a cork between fiber.

Paste can also optionally comprise other additives, such as the swelling agent of carbon black, barium sulfate and/or such as lignosulfonate and so on.Barium sulfate serves as the seed crystal for lead sulfate crystallization, the plumbous reaction to lead sulfate of excitation.Swelling agent helps prevent sulphate particles at the caking of negative plate, such as, forms the lump of lead sulfate in discharge process.

Such as, arrive about between 0.25% about 0.05% by the weighing scale of paste when swelling agent can be included in injection, or between about 0.09 to 0.2%, or between about 0.09 to 0.17%.Find, comprising expanding compounds at paste can have wholesome effect to CCA performance, but has counter productive to DCA performance.Usually, in paste, add the swelling agent of the concentration of about 0.2% or larger.Finding, to adopt when injecting by the weighing scale of paste about 0.09% to swelling agent concentration about between 0.15%, DCA and the CCA performance that can realize.

Paste also can comprise Ag, Bi, Zn or its any one compound, as anti-gasifying reagents.

Paste can have relatively low viscosity, such as, when being injected into electrode material, flows under gravity, and not on a horizontal surface from supporting.Preferably, paste has smectic viscosity.Find, when being injected into electrode, paste comprises (being greater than 0 still) when being less than the water by weight of 5%, realizes this point.

For helping paste to be injected in electrode material, such as can be less than 2kHz to paste or electrode material or both applyings, or being less than 1kHz, or the low frequency vibration within the scope of 50 to 500Hz.Also find, when mixing based on the particle of Pb, sulfuric acid and water to form paste, it is useful for helping mix by the vibration of paste in mixed process.

After battery unit or battery build, (the first charging and discharging cycle in initial cells forming process, in this process, active particle connection is formed), by building conductive frame, absorb the most of Pb in negative active material, to be structured in multiple length of several millimeters (string connecting the particle of perhaps 1,000 or more micron sizes end-to-end), battery to occur first and is formed.This stage also produces little PbSO ₄particle.Secondly, by these comparatively small-particle be attached to this conductive frame, to provide and received current.According to the present invention, Pb grid is replaced by minute yardstick fiber collector or is supplemented, and paste comprises PbSO ₄or PbO or Pb particle (or other particles of Pb compound), require in forming process, the Pb substantially only comprising the particle of Pb from these is attached to the nearest fiber in minute yardstick conductive current collector material.In forming process, make charging current periodically chopping be favourable.

Fiber current collector material can be supported by mechanical system, and supported mechanical framework also can provide each electrode to the electrical connection of battery unit or battery terminal (outer electrode joint).Such as, can one or more square of support set fluent material or rectangle adjacent layer, with by each side or external metallization framework between relative metal frame members on two opposite sides, form plane battery pole plate.Can alternatively, such as, the concentric cylindrical positive pole of each battery and negative plate can be included in the cylindrical section of the minute yardstick collector that arbitrary cylindrical end is supported by the metal framework of circle.Generally speaking, the form of ownership of aerial lug is all called as " pawl ".

Fig. 3 a schematically illustrates the carbon fiber electrode 50 of braiding, with the metal claw 51 that the outside of the electrode formed on carbon fibre material by compression casting is connected, Fig. 3 b shows difform pawl, and with tongue piece 53, and Fig. 3 c shows the cross section of the multilayer carbon fibre material with pawl.Pawl is made up of such as Pb or Pb alloy (being both called as Pb herein), but, can by preferably by be penetrated in fiber material and/or between another material of being electrically connected form.Preferably, pawl extends at the complete edge along electrode substantially.Such as, if electrode has square or rectangular shape, then pawl extends along the total length at an edge of electrode substantially.Preferably, pawl is substantially thicker unlike electrode material itself.

In certain embodiments, electrode material substantially all or at least most of silk/fiber spaning electrode extend continuously, the two ends of fiber or at least one end are electrically connected to metal framework or frame element.The textile fabric of continuous fiber is best.

Electrical connection between carbon fiber and pawl or conductive frame should be that minimum resistance connects, in a preferred form, each fibre end is all melted metal and surrounds, this deposite metal anchoring fiber end fibre end is electrically connected to metal framework physically in battery or cell architecture process.Metal framework or frame element can be formed to surround and to embed fiber ends itself by cooling deposite metal, the one or more edge band along electrode material.Optionally, fiber or fabric can extend beyond one or more frame element at one or more edge, to form another adjacent electrode or electrode section.Preferably, the place that whole or at least most of electrode fibers in a direction of material or face in axle are starting with fiber in active material is no more than 100mm apart to 10 millimeters of parts, or in two opposite edges of material, be electrically connected to metal frame members.This distance or the size in each current collector material cross section or area are determined primarily of the volume resistivity of the current collector material of most conducting direction.If only have fabric edge electric to be connected to metal frame members, preferably, this most conducting direction in fabric perpendicular to the edge calibration connected, to minimize all-in resistance.For allowing the highest current density in electrode not have great capacitance loss, the length of fabric from the edge connected can up to about 50 to 100mm.Metal framework alternatively can comprise the porose metallic plate of band in the one or both sides of material, the carbon fiber passing hole of the electric current only allowing carrying collect from the active material of its carrying or window.Such as, highly for the electrode framework of 200mm can comprise two windows, the height of each window is all 100mm, and conductive mesh is retained in around edge, to be 50mm from the distance farthest of any horizontal line (crossbar).For each in these window areas, carbon fabric can be dispersion, and is attached in metal water horizontal line and in edge.

Fig. 4 schematically illustrates electrode 55 from side, has the metal claw 56 similar with Fig. 3 along a marginal belt.In this embodiment, electrode on the one or both sides of carbon fibre material comprises the metal line or belt 57 being attached to electrode material 55 and pawl 56 conductively, to provide the extra grand yardstick current collection path except the minute yardstick path of the carbon fibre material via electrode itself.Metal line or belt can be attached to electrode material, such as, will the line of electrolyte be insoluble to by utilizing or the lead-acid battery binding material (such as resin, adhesive or embedding (potting) mixture) collector being fixed on other inertia of original position be sewed up or sewed up.In the fabrication process, metal line or belt can be pressed in electrode material.Alternatively, metal line or belt or similar thing can be welded to or be printed on carbon fiber electrode material.Metal line or belt can with bending arrangements on the one or both sides of carbon fibre material, as shown in the figure, extend continuously at the pawl 56 at an edge of electrode, in this edge, line or belt is by being embedded in pawl, be connected to pawl 56 conductively, and be positioned at or the edge at another interval towards electrode, as shown in the figure.Can alternatively, line or belt can extend between metal claw along the relative edge (or framework of surrounding them) of electrode.Can alternatively, equally, the independent length of line or belt can to extend to or towards another edge from pawl at of an electrode edge, or can alternatively, and equally, line or the grand conductor of described band can comprise the wire netting of the one or both sides being attached at carbon fibre material.

Fig. 5 is the schematic cross-section of electrode 55, the schematic cross-section of the electrode that the metal line or belt 56, Fig. 6 with the side being adhered to electrode material is made up of two-layer 55a and 55b carbon fibre material, with embedding or folder metal line or belt 56 in-between.In the fabrication process, can be compressed together with the carbon fiber of metal line or belt therebetween.

If be made of copper, should such as hot dipping, extruding be passed through, or plating, the plumbous or titanium of coating or be other metals of inertia at plumbic acid environment, in battery unit, prevent from comprising the metal line or belt of its any exposed distal ends or net or the oxidation of similar thing.The end of line or belt or net can terminate and be embedded in pawl or external frame.Importantly, when on the outer surface that collector is positioned at the electrode serving as negative pole, collector is prevented to be subject to the anodic oxidation of positive electrode.

Preferably, wire or band are along the length of electrode, and the width of spaning electrode has equal interval, without any crosspoint, as shown in Figure 3, occur or heat accumulation in specific region, and realize the uniform electric current collection of spaning electrode to prevent hot localised points.

Preferably, the volume of wire or band or grid or similar grand yardstick slip ring system is less than about 15% of electrode volume (getting rid of the metal framework of pawl or surrounding or similar thing).

In certain embodiments, electrode of the present invention, no matter be synthesis (also comprising metal grate) or nonsynthetic (not having metal grate), there is the thickness (being transverse to the length of electrode and width or face inside dimension) of any the inside dimension manyfold (such as 10,20,50, or 100 times and so on) being less than electrode.Thickness of electrode is passable, such as, is less than 5 or be less than 3mm.In the face of electrode in length and width dimensions each can, such as, be greater than 50 or 100mm.Such electrode has the plane form with low thickness.A kind of form of composite electrode of the present invention can comprise about 3.5mm or less, the metal grate of the thickness that all 0.5mm are according to appointment thick, and either side band is had an appointment the carbon fiber layer of 2mm or less, the thickness that all 0.3mm are according to appointment thick.

In preferred forms, electrode is plane substantially, and has, such as, be less than 100mm or be less than 70mm, or being less than 50mm, or the size of the metal claw for outside connection at least one edge along electrode of about 30mm or less (have or do not have grand yardstick collector).Alternatively, such as, such plane form can be formed as cylindrical electrode.

Heat treatment can be used as the carbon fibre material of electrode current collecting body material.Heat treatment also can improve the thermal conductivity of material, and this thermal conductivity should be enough to prevent the hot localised points on the electrode in use.Carbon fiber generally based on hydro carbons, and is heated to about 1100 DEG C or higher (" carbonization ") in the fabrication process.For being used as the current collector material in battery of the present invention or battery unit, carbon fibre material can be heated further, generally within the scope of 2200 to 2800 DEG C, being the region of aryl or graphite to amplify in carbon, thus improving conductivity.The heat treatment improving conductivity and/or thermal conductivity is passable, such as, adopts resistance-heated furnace, maybe can pass through arc discharge, wherein, in addition, and at least some or most agraphitic carbon in carbon fiber, and only a fraction of graphitic carbon can be evaporated.

Can heat-treat to reach enough temperature to carbon fiber current collector material, to improve its conductivity.Heat treatment can pass through arc discharge.In certain embodiments, by arc discharge, carbon fibre material is heat-treated, by reacting indoor moving carbon fibre material, mobile by the electric arc in gap between two electrodes, move through electrode, thus electric arc can be there is under the temperature of effective active material between electrode and material.In the figure 7, Ref. No. 1 represents the reactor chamber wherein producing electrical discharge arc.Electrode 2 and 3 reaches in reactor chamber 1, and usually installed by electrode-feeding mechanism 4, as known in the art, the position (location of anode and negative electrode can be put upside down) of electrode 3 (can be anode) and electrode 2 (can be negative electrode) can be adjusted to produce electric arc, and keep in operation or adjust electric arc when needed.Can also arrange that the cooling system 5 comprising the copper tube coil (water is by its circulation) being wound around each electrode is with cooling electrode.Carbon fibre material 8 through electrode 2 and 3, and reactor operating process in through electric arc, as shown in the figure.This is in fig. 8 than illustrating in more detail.Electric current should be enough to evaporate agraphitic carbon, but the local arc mode of attachment of not trigger destruction.The operation of suggestion between 10A and 20A.Material can enter reactor chamber by the slit 12 in reactor chamber, and is left by the similar exit slit 13 in the reactor chamber of the opposite side of electrode.Provide the mechanism by reactor chamber feedthrough material.Such as, in the operating process of reactor, can loosen substrate from the bobbin 9 driven by gear box, gear box utilizes suitable control system to be coupled to motor.In operation, the inside of reactor preferably equals atmospheric pressure or slightly higher than atmospheric pressure, by fume hood or filter or similar device, extracts the air-flow being exited reactor by slit 13.Such as, by introducing in check air-flow via an opening in the opening 11 in the base portion of reactor to reative cell 1 inside, make such as, such as the inert gas of nitrogen, argon or helium and so on pours in reative cell.Anode and to the bobbin preferably ground connection bringing row cutting into.For at substrate through any devices for taking-up collecting substrate after reactor chamber preferably also ground connection, reactor enclosure is ground connection also.With reference to figure 8, preferably, an electrode (in the drawings, being anode 3) is oriented to collide on substrate 8, and when moving through this electrode with convenient substrate, substrate is facing to the tension of this electrode, as schematically illustrated.Arc discharge can the most agraphitic carbon of evaporate carbon fiber material and only a fraction of graphitic carbon.The method can perform when existing metallic addition (such as Pb additive) of introducing.

Minute yardstick electrode according to the present invention with bore area region can provide enough electric capacity, to bring up to charging acceptance higher than electrochemically contributing.By acidic electrolysis bath get wet and the electrode zone that can be touched by acidic electrolyte bath electric capacity that the electric capacity that provides than the total surface area by the regular activated material in the negative pole of lead-acid battery can be contributed larger.It can have enough electrolyte bilayer capacity to absorb or to provide the high electric current in a few second.Can alternatively, battery of the present invention can comprise independent high surface area electrodes, and this electrode can comprise the carbon fibre material through electric arc process, as described herein, parallel with this or each battery cathode or positive pole, to increase or to improve electric capacity.

Such as can improve pore surface region by the heat treatment of arc discharge and improve electric capacity.At the forward direction carbon fibre material spraying Pb (NO of electric arc process ₃) ₂solution then this solution dry can improve surface area development (obviously by oxidation).Can alternatively, material can be activated by physical activation, such as by the steam at the temperature of about about 1000 DEG C or carbon dioxide, or by chemokinesis, such as, passes through aqueous slkali.Activate and usually in the material, or can produce the hole of nanoscale on the surface of the material, the most usually, largest diameter reaches the hole of 50nm.With the electric conductor that the material in the hole being widely less than about 1nm may not be.Surface area needed for Large Copacity can be provided from 1nm to the hole of about 10nm, but, also need well distributed hole higher than 10nm to provide the diffusivity easily of ion close, there to be sufficient electrolyte conductivity.In solid, also need enough conductivity.

In certain embodiments, carbon nano-tube (CNT) is attached in carbon fibre material.By the arc discharge process to carbon fibre material, or alternatively, by the presence of a catalyst, can carry out chemical vapor deposition at a lower temperature, produce CNT loading material.

As previously mentioned, (DCA is arrived by Axion thermometrically that the preferred form being applicable to hybrid power automobile battery unit and/or battery comprising electrode structure of the present invention can have improvement or higher DCA and CCA, CCA is basis, such as, SAE J357CCA thermometrically arrives), and/or can increase along with the quantity of charge-discharge cycle, and keep DCA or higher DCA to lead, and also can have low water consumption, and also can have improvement or the battery life of higher VED and/or improvement.The embodiment of battery unit of the present invention or battery, such as, after 5000 or 10000 cycles, keeps the DCA of the initial DCA of at least 70% or 80% or 90% (when first time is full of electricity).The embodiment of battery unit of the present invention or battery can use Axion DCA to test, and 10,000 cycle kept per charging stage at least 0.6 or 0.7 or the average DCA of 0.8A/Ah.The capacity of battery is with ampere/hour tolerance, utilance is that actual battery capacity is divided by theoretical maximum capacity, the embodiment of battery unit of the present invention or battery can have the utilance of increase, the utilance of such as at least 55%, 60%, 70% or 80% or higher.

Example

What be given as examples below further illustrates the present invention to the description of experimental work.In some examples, refer to DCA test, Figure 10 shows DCA testing algorithm, according to this algorithm, carry out two-forty to each battery dynamically to charge acceptance test (DCAT), this test is designed to simulation microring array car to the stopping/startup demand of its battery.DCAT test result curve is acceleration, the destructive test in useful life of the battery to the state remaining on constant charging, guarantee that DCAT test is independent of test macro and the calibration problem that is associated with this system, so avoids the calibration problem be usually associated with other life test agreements.The DCAT used tests the Axion DCAT test result curve followed on Cadex C8000 test macro, and wherein, test result curve comprises the following steps:

0.51C discharges 60s

3.15C pulsed discharge 1s

10s stop (at the end of, measure PDRV (after electric discharge, stopping voltage))

The dynamic charge cycle of adjustment 1.05C, to be fixed on given set point by PDRV

10s stops.

Repeat this circulation summary described to 30, the cycle count of 000, this is converted into typical 6 time-of-week sections, although this time period depends on battery performance.Every 5000 circulations, charging completely, is next deep discharge, measurement electrode capacity.For being tested by this, battery unit needs through DCAT test at least 30,000 time, and to keep capacity at least 2Ah.30,000 circulation is the representative of the battery life of the micro-hybrid type of about 3 years.

Example 1: with the composite electrode-N371 of the carbon fiber paper of Pb grid

Method: utilize thickness for 3mm, ~ 6% carbon volume fraction, proportion ~ 312g/m ², and the carbon fiber paper carbon pad of the fibre length of 25mm (Z-Mat that Zoltek produces), manufacture electrode.Two panels is cut into size 44mm*70mm, then splits into thinner layer, to produce each layer of average thickness 0.26mm.Electrode is manufactured by being placed on by the one deck in these carbon fiber layers on each surface in two surfaces of lead grid lattice.

Utilize 23.2g lead oxides (in 2009, lead oxides in batch from Exide buys), 4.0g dilute sulfuric acid, 2.7g Vanisperse A (swelling agent) aqueous solution, with enough Vanisperse A, to realize 0.10wt% in the paste prepared, and 0.187g barium sulfate, prepare paste.In ultrasonic bath, mixing paste, reaches 2 minutes (at 23 DEG C of case temperature, 53kHz frequency).A fibrage in fibrage is placed on flat board, then, lead grid lattice is placed on fibrage.Pb grid has thickness 2.02mm, length 66.3mm, and width 44.2mm, open volume divides rate ~ 81.6%.Paste is spread upon lead grid lattice on the surface, until paste is evenly distributed on the surface, whole lattice vacancies is all filled with paste.Then, the grid surface smearing paste scatters paste unnecessary fully with partly fiberfill fibers layer, then, by placed on it for the second carbon fiber layer.Scatter paste further on the top to obtain level and smooth and uniform surface.Unnecessary paste is removed from the two sides of electrode and side.The gross thickness of having smeared the electrode of paste is roughly 2.60mm.

The total amount being loaded into the wet material in composite electrode is 24.41g, and wherein, the capacity (low current electric discharge) of realization is 2.695Ah (that is, the theoretical capacity of 60%).Suppose that paste enters/be distributed in grid and fibrage equably, the NAM of 19.8% is distributed in the fibrage of electrode, and remainder is in lead grid lattice.At the fully charged state of electrode, average activity Substance P b and carbon volume ratio are 10.03.Equispaced between carbon fiber is about 23 microns.Subsequently, at ambient temperature (18 DEG C – 24 DEG C) air-dry 24 hours, 1.15sg H is being comprised ₂sO ₄electrolyte battery unit in assembling smeared the electrode of paste, one, every side (40%SOC) positive pole.Under ambient temperature (18 DEG C – 24 DEG C), infiltrate battery unit 24 hours, and perform battery standard formation.

Method of testing and result: electrolyte is replaced with 1.28sg H ₂sO ₄, and stable under four cycles of low current electric discharge (0.06C) before being sent to two-forty DCA.According to test as described above and as shown in Figure 10, two-forty is performed to battery unit and dynamically to charge acceptance test (HR-DCAT).Be shown in the following Table 1 result.

Example 2: with the composite electrode-N359 of the carbon fiber textile fabric through electric arc process of Pb grid

Method: electrode is by carbon fibre fabric of weaving, and the weaving carbon fiber tape (being manufactured by Taiwan TaiCarbon) based on PAN [polyacrylonitrile] is made.Fabric is processed in general manner, as described in reference to Figure 8 in electric arc.This fiber through electric arc process has 136g/m ²proportion, 0.38mm is thick, and has ~ 20% carbon volume fraction.Two panels is cut into the size of 44mm*70mm through the fiber of electric arc process.One block of fiber through electric arc process is placed on ultrasonic wave plate, and by placed on it for lead grid lattice.Pb grid has thickness 1.94mm, length 66.7mm, and width 44.4mm, open volume divides rate ~ 81.1%.Prepare paste, smear electrode with paste, and use second layer carbon fibre fabric to build, all as described in example 1.The gross thickness of having smeared the electrode of paste is roughly 3.6mm.

The total amount being loaded into the wet mass matter in composite electrode is 28g, and wherein, the capacity (low current electric discharge) of realization is 2.99Ah (that is, the theoretical capacity of 60%).Suppose that paste enters equably/is distributed in grid and fibrolaminar available voidage, the NAM of 28.1% is distributed in the carbon fiber layer of composite electrode, and remainder is in lead grid lattice.Under the fully charged state of electrode, average activity Substance P b and carbon volume ratio are 3.20.Equispaced between carbon fiber is about about 15 microns.

Subsequently, air-dry electrode, is assembled in battery unit, and battery unit maintenance infiltrates, and then, performs in the battery and forms charging and stablize, all as described in example 1.

Method of testing and result: electrolyte is replaced with 1.28sg H ₂sO ₄, and stable under four cycles of low current electric discharge (0.06C) before delivering to two-forty DCA.According to test as described above and as shown in Figure 10, two-forty is performed to battery unit and dynamically to charge acceptance test (HR-DCAT).Be shown in the following Table 1 result.

The result of the DCAT test of the electrode of statement in the more superincumbent example 1 and 2 of table 1 –.

Example 3: through the non-synthetic electrode of the carbon felt of electric arc process, active material/carbon volume ratio ~ 2.698-N363-see Fig. 1 and 2

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.Felt is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.5mm, and carbon volume fraction ~ 7%.Material after electric arc process has 217g/m ²proportion, 2.4mm is thick, and has ~ 6% carbon volume fraction.

The method that the paste of individual layer felt is smeared is different from the method for multi-layered textile fabric as described above.From the lead oxides of 19.5g (in 2009, lead oxides in batch from Exide buys) prepare paste to the identical composition recorded in example 1 with 2 above, and in ultrasonic bath, follow same mixture process under lower the same terms.Then, carbon felt member is placed in the plate for smearing paste.Then, the paste prepared above is dispersed on carpet veneer, until paste is evenly distributed on the surface.Then, felt member is placed on ultrasonic vibration plate, the surface of not smearing paste is faced up, and use flexible plastic spatula that paste is distributed in this on the surface.Smear in process at paste, ultrasonic vibration continues ~ 50 seconds.(use the ultrasonic vibration plate manufactured by Skymen Cleaning Equipment Shenzhen Co.Ltd, use the current class on ultrasonic plate to be 1.75A, electrodes makes it cover a transducer point on lamination).While ultrasonic wave work, overturn several times by the electrode smearing paste, until paste seems to distribute equably from the teeth outwards, and wherein most of paste has infiltrated in felt.

The total amount being loaded into the wet mass matter in composite electrode is 19.5g, and wherein, the capacity (low current electric discharge) of realization is 2.4Ah (that is, the theoretical capacity of 66%).

Electrode activity (coating) area size of having smeared paste is length 67.4mm, width 45.6mm, thickness 2.44mm.It is 1.91g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode smears the density of paste) ³.Under the fully charged state of electrode, active material Pb and carbon volume ratio are 2.698.Equispaced between carbon fiber is about 36 microns.

Subsequently, air-dry electrode, is assembled in battery unit, and battery unit keeps infiltrating, and then, performs and forms charging, all as described in example 1 in battery unit.

Method of testing and result: described by example 1 and 2, test electrode, the results are shown in table 2.

Example 4: through the non-synthetic electrode of the carbon felt of electric arc process, active material/carbon volume ratio ~ 4.52-N439-see Figure 12

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD 2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.Felt is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.6mm, and carbon volume fraction ~ 6%.Material after electric arc process has 197g/m ²proportion, 2.33mm is thick, and has ~ 6% carbon volume fraction.

Use the copper wire of the lead plating that diameter is 0.38mm as the extra collector for electrode above.Before insertion pawl, in a zigzag manner, along the length of felt, these are placed on felt on the surface by artificially, and wherein vertical strip is separated along even width.Pawl is inserted in felt, so that the top of each word of copper wire to be immersed in pawl and is attached to pawl.

Smear the method for paste:

Utilize 23g lead oxides (in 2009, lead oxides in batch from Exide buys), 1.5g dilute sulfuric acid, 0.023g Vanisperse A (swelling agent) is to realize 0.1% swelling agent in paste, and 0.184g barium sulfate, prepare paste.Prepared by paste and smear, following the same mixture process as described in the example before N363 and N364.In the process of smearing, ultrasonic vibration continues ~ 1.30 minutes.(use the ultrasonic vibration plate manufactured by Skymen Cleaning Equipment Shenzhen Co.Ltd, use the current class on ultrasonic plate to be 1.75A, and electrodes make a transducer point on its overlay).While ultrasonic wave work, overturn several times by the electrode smearing paste, distribute equably from the teeth outwards until observe paste, wherein most of paste has infiltrated in felt.

The total amount being loaded into the wet mass matter in electrode is 24.62g, and wherein, the capacity (low current electric discharge) of realization is 3.077Ah (that is, the theoretical capacity of 62%).The electrode activity region (being coated with cream region) of having smeared paste is of a size of length 59mm, width 45mm, thickness 2.7mm.It is 2.63g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode is coated with cream density) ³.Under the fully charged state of electrode, active material Pb and carbon volume ratio are 4.52.Equispaced between carbon fiber is about 40 microns.

Subsequently, under ambient temperature (18 DEG C – 24 DEG C) air-dry 24 hours, 1.15sg H is being comprised ₂sO ₄electrolyte battery unit in assembling be coated with the electrode of cream, one, every side (40%SOC) positive pole.Under ambient temperature (18 DEG C – 24 DEG C), battery unit infiltrates 24 hours.Then, be similar to for example 1, perform and form charging and stablize.

Test and result: then, transfer battery unit, test with the SAE J537 using industry known, at room temperature and-18 DEG C at operative norm start test (CCA).

Example 5: through the non-synthetic electrode of the carbon felt of electric arc process, have the extra collector (total length, roughly 1m) of the copper cash of lead plating on the surface at felt, active material/carbon volume ratio ~ 3.63-N411-is see Fig. 1 and 13

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.Felt is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.5mm, and carbon volume fraction ~ 7%.Material after electric arc process has 190g/m ²proportion, 2.24mm is thick, and has ~ 6% carbon volume fraction.

Use the extra collector of copper cash as electrode above of the lead plating that diameter is 0.38mm.In a zigzag manner, along the length of felt, these are placed on felt on the surface by artificially, and vertical strip is along interval, even width ground.

The preparation of paste is identical with the process of smearing with N363 as described above, and difference is use 1 point of sonication times of 17 seconds.

The total amount being loaded into the wet mass matter in electrode is 17.08g, and wherein, the capacity (low current electric discharge) of realization is 2.15Ah (that is, the theoretical capacity of 67.7%).The electrode activity region being coated with cream is of a size of length 60.5mm, width 44.1mm, thickness 3.6mm.It is 1.28g/cm that the lead of the every volume realized is loaded into (electrode based on the material being loaded into electrode is coated with cream density) ³.At the fully charged state of electrode, active material Pb and carbon volume ratio are 3.63.Equispaced between carbon fiber is about 40 microns.

Subsequently, electrode under ambient temperature (18 DEG C – 24 DEG C) air-dry 24 hours, is then comprising 1.15sg H ₂sO ₄electrolyte battery unit in assemble this painting cream electrode, one, every side (40%SOC) positive pole.Under ambient temperature (18 DEG C – 24 DEG C), battery infiltrates 24 hours.Then, be similar to example 1 ground perform formation charging and stablize.

Test and result: then, battery unit is conveyed at room temperature to perform and starts ampere test, is then conveyed to and performs water consumption test (Tafel).At Fernandez, M., Atanassova, P., ALABC Project ref 1012M report no.1, in Mar-Aug2011, describe standard Tafel test.

Example 5: through the non-synthetic electrode of the weaving carbon fiber of electric arc process, active material/carbon volume ratio ~ 0.88-N305---see Figure 14

Method: electrode is made up of the weaving weaving carbon fiber tape of carbon fibre fabric based on PAN [polyacrylonitrile] (being manufactured by Taiwan TaiCarbon).Fabric is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.This fiber through electric arc process has 181g/m ²proportion, 0.58mm is thick, and has ~ 18.4% carbon volume fraction.Four fibers through electric arc process are cut into the size of 44mm*70mm.

Before electric arc process, utilize Pb (NO ₃) ₂the complete wetted material of the aqueous solution, and dry a whole night, so that the Pb of deposition quality 2%.

Then the layer that assembling four is such, overlapped so that they all bond to lead gasket, formed with in their end and connect pawl.The weldment (50%Sn, 50%Pb) of the 15mm*44mm of graduation is placed in three gap locations between four layers, also has two on two outer surfaces.Then, the outside of metallic lead band (0.6mm is thick) wide for 25mm around the end of four layers is folded, covers the top 10mm part of folded every one deck.Under inert gas conditions, this structure is placed in can (box of filling with nitrogen), and is placed in baking box at 200 DEG C ~ 1 hour.Lead covering is being extruded, with in carbon fiber and the contact that provides between melting solder and lead after taking out from baking box.So, form pawl on the top of electrode, connect and fixed carbon tissue layer, carbon fabric layer can be movable for further process neatly.

For manufacturing active material, mix PbSO with low-concentration sulfuric acid (proportion <1.05) ₄powder (the mean size 4-5 μm after grinding), to make the PbSO of quality 77.3% ₄paste.Pawl is above placed on flat board.Pawl is placed in be coated with cream plate on, from three layers above plate is fixed, and the 4th layer onboard.The 4th layer on flat board is smeared paste.Then, lower one deck is released on ground floor.The surface of the second layer distributes paste, until realize smooth surface.For the ensuing two-layer process repeated above.Then, overturn total onboard, then utilize ultrasonic vibration, cause paste to penetrate and distribute equably, until all fibres space is all filled.This realizes therebetween in the sonication times section of about 30s.

The total amount being loaded into the wet quality in electrode is 15.6g, and wherein, the capacity (low current electric discharge) of realization is 2.33Ah (that is, the theoretical capacity of 62%).

The electrode activity region (being coated with cream region) being coated with cream is of a size of length 61mm, width 44.7mm, thickness 2.22mm.It is 1.402g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode is coated with cream density) ³.At the fully charged state of electrode, active material Pb and carbon volume ratio are 0.88.Equispaced between carbon fiber is about 17 microns.

Subsequently, under ambient temperature (18 DEG C – 24 DEG C) air-dry 24 hours, and comprising 1.15sg H ₂sO ₄electrolyte battery unit in assembling be coated with the electrode of cream, one, every side (40%SOC) positive pole.Under ambient temperature (18 DEG C – 24 DEG C), battery unit infiltrates 24 hours.Then, be similar to example 1 ground perform formation charging and stablize.

Test and result: then, send to battery unit at room temperature to perform and start ampere test, perform water consumption test (Tafel) more afterwards to electrode 411.At Fernandez, M., Atanassova, P., ALABC Project ref 1012M report no.1, in Mar-Aug2011, describe standard Tafel test.

Example 6: through the non-synthetic electrode of the carbon felt of electric arc process, active material/carbon volume ratio ~ 2.63-N356-see Figure 16

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.Felt is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.5mm, and carbon volume fraction ~ 7%.Material after electric arc process has 217g/m ²proportion, 2.47mm is thick, and has ~ 6.3% carbon volume fraction.

The preparation of paste with smear the same for the process of N363 as described above, difference is use 1 point of sonication times of 26 seconds.

The total amount being loaded into the quality in electrode is 15.60g, and wherein, the capacity (low current electric discharge) of realization is 1.93Ah (that is, the theoretical capacity of 67%).The electrode activity region of having smeared paste is of a size of length 61.02mm, width 44.77mm, thickness 2.34mm.It is 1.75g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode is coated with cream density) ³.At the fully charged state of electrode, active material Pb and carbon volume ratio are 2.63.Equispaced between carbon fiber is about 37 microns.

Subsequently, in ambient temperature (18 DEG C – 24 DEG C) leeward dry cell 24 hours, then 1.15sg H is being comprised ₂sO ₄electrolyte battery unit in assembling be coated with cream electrode, one, every side (40%SOC) positive pole.Under ambient temperature (18 DEG C – 24 DEG C), battery infiltrates 24 hours.Then, be similar to example 1 ground perform formation charging and stablize.

Test and result: then, transfer battery unit, to carry out the test of starting ampere room temperature and-18 DEG C, then sends to and carries out HR-DCAT test.In table 2 and Figure 16, result is shown.

Example 7: through the non-synthetic electrode of the carbon felt of electric arc process, active material/carbon volume ratio ~ 3.68---N409

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.Felt is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.5mm, and carbon volume fraction ~ 7%.Material after electric arc process has 183g/m ²proportion, 1.98mm is thick, and has ~ 6.6% carbon volume fraction.

Use the extra collector of copper cash as electrode above of the lead plating that diameter is 0.38mm.Just, before insertion pawl, in a zigzag manner, along the length of felt, these copper cash are placed on felt on the surface to make vertical strip separate along even width by artificially.Pawl is inserted in felt, and (word place) is attached to pawl so that the top of each line of copper cash.

The preparation of paste is with to smear as described above for N363 the same, and difference is use 1 point of sonication times of 10 seconds.

The total amount being loaded into the wet quality in electrode is 17.79g, and wherein, the capacity (low current electric discharge) of realization is 2.03Ah (that is, the theoretical capacity of 61%).The electrode activity region of having smeared paste is of a size of length 63.5mm, width 44.85mm, thickness 2.71mm.It is 1.66g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode is coated with cream density) ³.At the fully charged state of electrode, active material Pb and carbon volume ratio are 3.68.Equispaced between carbon fiber is about 45 microns.

Subsequently, under ambient temperature (18 DEG C – 24 DEG C), air-dry electrode 24 hours, is then comprising 1.15sg H ₂sO ₄electrolyte battery unit in assembling smeared the electrode of paste, one, every side (40%SOC) positive pole.Under ambient temperature (18 DEG C – 24 DEG C), battery unit infiltrates 24 hours.Then, be similar to example 1 ground perform formation charging and stablize.

Test and result: then, send to battery unit and at room temperature carry out standard starting test, then carry out HR-DCAT test.Result is described in table 2 and Figure 15.

Example 8: through the non-synthetic electrode of the carbon felt of electric arc process, has the extra collector (total length is 1m roughly) of the copper cash of lead plating on the surface at felt, active material/carbon volume ratio ~ 3.797-N410-is see Figure 18

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.Felt is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.5mm, and carbon volume fraction ~ 7.1%.Material after electric arc process has 183g/m ²proportion, 1.98mm is thick, and has ~ 6.6% carbon volume fraction.

Use the extra collector of copper cash as electrode above of the lead plating that diameter is 0.38mm.In a zigzag manner, along the length of felt, these copper cash are placed on felt on the surface by artificially, and wherein, before insertion pawl, vertical strip is along interval, even width ground.Pawl is inserted in felt, is attached to pawl with the top of the word of each making copper cash.

The preparation of paste with smear and the same for N363 as described above, difference is use 1 point of sonication times of 11 seconds.

The total amount being loaded into the wet quality in electrode is 17.66g, and wherein, the capacity (low current electric discharge) of realization is 2.11Ah (that is, the theoretical capacity of 64.4%).The electrode activity region (being coated with cream region) of having smeared paste is of a size of length 61.71mm, width 44.34mm, thickness 2.78mm.It is 1.67g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode is coated with cream density) ³.At the fully charged state of electrode, active material Pb and carbon volume ratio are 3.797.Equispaced between carbon fiber is about 45 microns.

Subsequently, under ambient temperature (18 DEG C – 24 DEG C), air-dry electrode 24 hours, is comprising 1.15sg H ₂sO ₄electrolyte battery unit in assembling smeared the electrode of paste, one, every side (40%SOC) positive pole.Under ambient temperature (18 DEG C – 24 DEG C), battery unit infiltrates 24 hours.Then, be similar to example 1 ground perform formation charging and stablize.

Test and result: then, battery is conveyed to and at room temperature carries out standard starting test, then sends to and carries out Axion-DCA test.

Example 9: through the non-synthetic electrode (thickness ~ 1.3mm) of the carbon felt of electric arc process, have the extra collector (total length is 1m roughly) of the copper cash of lead plating on the surface at felt, active material/carbon volume ratio ~ 4.893-N441-is see Fig. 1

This electrode utilizes the felt JX-PCF through electric arc process manufactured by Heilongjiang J & X Co., Ltd. China, utilizes carbon fiber layer to manufacture.Felt has 508g/m ²proportion, the thickness of 4mm, and carbon volume fraction ~ 7.5%.Material is split as thinner band (using sharp blade artificially to cut off), and carries out electric arc process, as described in example above.Material after electric arc process has 144g/m ²proportion, 1.3mm is thick, and has ~ 6.4% carbon volume fraction.

Use the extra collector of copper wire as electrode above of the lead plating that diameter is 0.38mm.Before placement pawl, in a zigzag manner, along the length of felt, these copper wires are placed on felt on the surface by artificially, and wherein vertical strip is along interval, even width ground.Use solder (50%Sn with 50%Pb) in the mode identical with example 5 above, electrode prepares pawl for this reason, guarantees that the top of the word of each of copper wire to be immersed in pawl and to be attached to pawl.

Paste preparation with smear and identical for N363 as described above, difference is use 1 point of sonication times of 48 seconds.

The total amount being loaded into the wet quality in electrode is 16.11g, and wherein, the capacity (low current electric discharge) of realization is 2.052Ah (that is, the theoretical capacity of 63%).The electrode activity region of having smeared paste is of a size of length 59.8mm, width 44.9mm, thickness 1.78mm.It is 2.64g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode is coated with cream density) ³.Under the fully charged state of electrode, active material Pb and carbon volume ratio are 4.893.Equispaced between carbon fiber is about 23 microns.

Table 2

Example 10: through the non-synthetic electrode of the carbon felt of electric arc process, active material/carbon volume ratio ~ 2.53-N387

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.Felt is processed in general manner, as described in front reference diagram 7 and 8 in electric arc.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.5mm, and carbon volume fraction ~ 7%.Material after electric arc process has 203g/m ²proportion, 2.25mm is thick, and has ~ 6.4% carbon volume fraction.

The preparation of paste with smear and the same for N363 as described above, difference prepares Vanisperse A ^tMsolution to realize the Vanisperse A of quality 0.07% in final paste ^tM, and use 1 point of sonication times of 23 seconds.

The total amount being loaded into the wet quality in electrode is 14.2g, and wherein, the capacity (low current electric discharge) of realization is 1.68Ah (that is, the theoretical capacity of 64%).

The electrode activity area size of having smeared paste is: length 67.4mm, width 44.8mm, thickness 2.46mm.It is 1.38g/cm that the lead of the every volume realized is loaded into (electrode based on the quality being loaded into electrode is coated with cream density) ³.At the fully charged state of electrode, active material Pb and carbon volume ratio are 2.53.Equispaced between carbon fiber is about 39 microns.

Subsequently, air-dry electrode, is assembled in battery unit, makes battery unit keep infiltrating, and then, performs and forms charging, all as described in example 1 in battery unit.Then, battery unit is sent at room temperature and at-18 DEG C operative norm starting current test.

Example 11: through the non-synthetic electrode of the carbon felt of electric arc process, active material/carbon volume ratio ~ 2.696-N392

Method: electrode is made up of the carbon fiber layer (the Sigracell KFD2.5EA manufactured by German SGL Carbon Company) of the carbon felt through electric arc process.In electric arc, felt is processed roughly as described in front reference diagram 7 and 8.Felt before electric arc process has 248g/m ²proportion, the thickness of 2.5mm, and carbon volume fraction ~ 7%.Material after electric arc process has 203g/m ²proportion, 2.25mm is thick, and has ~ 6.4% carbon volume fraction.

Preparing paste like that and smearing paste as described above for N363, difference prepares Vanisperse A ^tMsolution is to make to realize the Vanisperse A by quality 0.25% in final paste ^tM, and use 1 point of sonication times of 23 seconds.

The total amount being loaded into the wet quality in electrode is 15.33g, and wherein, the capacity (low current electric discharge) of realization is 1.83Ah (that is, the theoretical capacity of 64%).

The amount of the sulfuric acid used in example 12 – paste

Add small lot paste, it is by lead monoxide (quality accounts for 97%) and the plumbous particle of (3%) and the suspension-turbid liquid of water, and the acid formation of increase.The Solid Suspension of 13.0g, in the water of 3.65g, realizes the solid masses point rate of 78% and the volume fraction of about 27%.This is the slurry freely precipitated, and is difficult to evenly suspend, and is difficult to be distributed in felt pan equably.Vibration (ultrasonic wave) can not improve attribute, can not help infiltration.The pH value of the liquid balanced with solid is 10.Adding a small amount of acid, with when observing slight creaminess, making acid reach quality about 0.12%, pH value about 9 to 9.5.Add the pH value that 0.5% causes creamy paste and 8.5 to 9 further to.Adding further acid makes pH be down to 8.0 of buffering.

Then, utilize same solid as above point rate to make several independent mixture, be penetrated into felt attempted for comparatively high acid concentration after a while by hyperacoustic dispersion.When quality 0.24% sour, paste material does not almost have stability in spatula, but paste penetrates well (some appears at the opposite side of the thick felt of 2.3mm).When felt penetrate and high be loaded into both become may time, best sour addition is about 1.0%.Along with acid increases, paste becomes more viscous, and 2.28% time, paste can utilize spatula to smear, but after ultrasonic wave, it remains in the outside of felt pan in a large number, permeates bad and rapid draing.

Aforesaid content describes the present invention, comprises the form of its first-selection, will it will be apparent to those skilled in the art that modification is intended to be included in the scope of subsidiary claim definition.

Claims

1. a lead-acid battery or battery unit, comprise at least one (non-synthetic or synthesis) electrode, described electrode comprises conductive fiber material as collector, and described conductive fiber material has and is loaded into than (respectively at least major part of electrode) with the quality of conductive fiber quality at least about the voidage (being plumbous and the volume fraction that occupies of hole between conductive fiber) of 0.3 and the lead (in any form) when being converted to volume ratio in the scope of 0.7:1 to about 15:1 when being full of electricity.

2. a lead-acid battery or battery unit, comprise at least one (non-synthetic or synthesis) electrode, described electrode comprises conductive fiber material as collector, and described conductive fiber material has and is loaded into than (respectively at least major part of electrode) with the quality of conductive fiber quality at least about the voidage (being plumbous and the volume fraction that occupies of hole between conductive fiber) of 0.3 and the lead (in any form) when being converted to volume ratio in the scope of about 1:1 to about 10:1 when being full of electricity.

3. according to lead-acid battery according to claim 1 or claim 2 or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and described conductive fiber material has when being full of electricity about 0.3 and voidage about between 0.9.3

4. according to lead-acid battery according to claim 1 or claim 2 or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and conductive fiber material comprises when being full of electricity about 0.3 and voidage about between 0.85.

5. according to lead-acid battery according to claim 1 or claim 2 or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and conductive fiber material has when being full of electricity about 0.3 and voidage about between 0.80.

6. according to lead-acid battery according to claim 1 or claim 2 or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and conductive fiber material has when being full of electricity about 0.7 and voidage about between 0.95.

7. according to lead-acid battery according to claim 1 or claim 2 or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and conductive fiber material has when being full of electricity about 0.5 and voidage about between 0.98.

8. according to lead-acid battery according to claim 1 or claim 2 or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and conductive fiber material has when being full of electricity about 0.8 and voidage about between 0.95.

9. the lead-acid battery according to any one in claim 1 to 8 or battery unit, comprise at least one electrode, and wherein, when being converted to Pb, the volume of active material and conductive fiber is loaded into ratio at about 1:1 with about between 7:1.

10. the lead-acid battery according to any one in claim 1 to 8 or battery unit, comprise at least one electrode, and wherein, when being converted to Pb, the volume of active material and conductive fiber is loaded into ratio at about 1.5:1 with about between 4:1.

11. lead-acid batteries according to any one in claim 1 to 8 or battery unit, comprise at least one electrode, and wherein, when being converted to Pb, the volume of active material and conductive fiber is loaded into than at about 2:1 with about between 3:1.

12. 1 kinds of lead-acid batteries or battery unit, comprise at least one (non-synthetic or synthesis) electrode, described electrode comprises conductive fiber material as collector, described conductive fiber material has the voidage (being the volume fraction that the hole between lead and conductive fiber occupies) when being full of electricity at least about 0.3, and the loading of the plumbous volume of (in any form) and the volume of conductive fiber is than (respectively at least major part of electrode), they define a bit together in voidage (x-axis) and the volume of lead and the figure of the loading of the volume of conductive fiber than (y-axis), this point drop on by described figure with the line of slope about-1/0.02 from the x-axis space angle value of about 98%, with in the region that described figure defines with slope about-1/0.3 another line from the x-axis space angle value of about 70%.

13. lead-acid battery according to claim 12 or battery units, wherein, voidage than together with defines a bit with plumbous volume with the loading of the volume of conductive fiber on described figure, and this point drops on in the line of slope about-1/0.03 from the x-axis space angle value of about 97% and the region that defines with slope about-1/0.2 another line from the x-axis space angle value of about 80%.

14. lead-acid battery according to claim 12 or battery units, wherein, voidage than together with defines a bit with plumbous volume with the loading of the volume of conductive fiber on described figure, and this point drops on in the line of slope-1/0.04 from the x-axis space angle value of 96% and the region that defines with slope about-1/0.15 another line from the x-axis space angle value of 85%.

15. 1 kinds of lead-acid battery or battery units comprising at least one (non-synthetic or synthesis) electrode, described electrode comprises carbon fibre material as collector, this carbon fibre material has the carbon fibrous body integration rate being less than 40%, and the volume of lead (in any form) being greater than 0.5 with the loading of the volume of carbon fiber than (respectively at least major part of electrode, more preferably, substantially all on electrode).

16. lead-acid battery according to claim 15 or battery units, have the carbon fibrous body integration rate being less than 30%, and are greater than the volume of lead of 0.7 and the loading ratio of the volume of carbon fiber.

17. lead-acid battery according to claim 15 or battery units, have the carbon fibrous body integration rate being less than 20%, and are greater than the volume of lead of 1:1 and the loading ratio of the volume of carbon fiber.

18. lead-acid batteries according to any one in claim 1 to 17 or battery unit, wherein, be interposed between between the average fiber between the fiber in conductive fiber material between about 1 and about 5 fiber diameter.

19. lead-acid batteries according to any one in claim 1 to 18 or battery unit, wherein, between the average fiber between the fiber in conductive fiber material, interval is less than about 50 microns.

20. lead-acid batteries according to any one in claim 1 to 18 or battery unit, wherein, the equispaced in conductive fiber material is less than about 20 microns.

21. lead-acid batteries according to any one in claim 1 to 20 or battery unit, wherein, fiber diameter is less than about 20 microns.

22. lead-acid batteries according to any one in claim 1 to 20 or battery unit, wherein, conductive fiber material comprises carbon fibre material.

23. lead-acid battery according to claim 22 or battery units, wherein, carbon fibre material comprises non-thermoplastic carbon fibre material.

24. lead-acid battery according to claim 23 or battery units, wherein, described non-thermoplastic carbon fiber comprises carbon fiber felt materials.

25. according to claim 23 or lead-acid battery according to claim 24 or battery unit, wherein, by splitting thicker non-woven material in face, produces the non-thermoplastic carbon fibre material that thickness is about 2.5mm or less.

26. lead-acid battery according to claim 22 or battery units, wherein, carbon fibre material comprises weaving carbon fibre material.

27. lead-acid battery according to claim 22 or battery units, wherein, carbon fibre material comprises weaving carbon fiber material.

28. lead-acid batteries according to any one in claim 22 to 27 or battery unit, wherein, carbon fibre material is made up of carbon fibre tow, carbon fibre tow is pulled off that each continuous fibers are split into shorter silk, and at the end of the longitudinal separating wire of each breakpoint, to reduce the silk number of carbon fibre tow.

29. lead-acid batteries according to any one in claim 22 to 28 or battery unit, wherein, conductive fiber material comprises the silk of average length in about 3 scopes to about 50mm.

30. lead-acid batteries according to any one in claim 22 to 30 or battery unit, wherein, carbon fibre material has the average thickness being less than 5mm of length in the primary flat of material and width dimensions and the described primary flat perpendicular to material.

31. lead-acid batteries according to any one in claim 22 to 30 or battery unit, wherein, carbon fibre material has the average thickness being less than 3mm of length in the primary flat of material and width dimensions and the described primary flat perpendicular to material.

32. lead-acid batteries according to any one in claim 22 to 30 or battery unit, wherein, carbon fibre material has the average thickness being less than 2mm of length in the primary flat of material and width dimensions and the described primary flat perpendicular to material.

33. lead-acid batteries according to any one in claim 22 to 32 or battery unit, wherein, heat-treated carbon fibre material by arc discharge.

34. lead-acid battery according to claim 33 or battery units, wherein, by causing relative motion between the electric arc in the gap between described carbon fibre material and two electrodes, or make it through an electrode thus electric arc is present between electrode and carbon fibre material, by arc discharge, carbon fibre material is heat-treated.

35., according to claim 33 or lead-acid battery according to claim 34 or battery unit, wherein, are heat-treated carbon fibre material by arc discharge, with most of agraphitic carbon of evaporate carbon fiber material and only sub-fraction graphitic carbon.

36., according to claim 33 or lead-acid battery according to claim 34 or battery unit, wherein, heat-treat carbon fibre material, with the sub-fraction of the graphitic carbon of evaporate carbon fiber material.

37. lead-acid batteries according to any one in claim 22 to 36 or battery unit, wherein, carbon fibre material comprises or derives from artificial silk, polyacrylonitrile, phenolic resins or resin material.

38. lead-acid batteries according to any one in Claim 1-3 7 or battery unit, wherein, conductive fiber material comprises unique collector of this electrode or each electrode.

39. lead-acid batteries according to any one in Claim 1-3 7 or battery unit, wherein, this electrode or each electrode also comprise metal grate.

40. according to lead-acid battery according to claim 39 or battery unit, and wherein, conductive fiber material comprises individual layer in the side of metal grate.

41. according to lead-acid battery according to claim 39 or battery unit, and wherein, at least side of conductive fiber material in the both sides of metal grate comprises multiple layer.

42. lead-acid batteries according to any one in claim 39 to 41 or battery unit, wherein, the active material of at least 20% is in conductive fiber material.

43. lead-acid batteries according to any one in claim 39 to 41 or battery unit, wherein, the active material of at least 40% is in conductive fiber material.

44. lead-acid batteries according to any one in claim 39 to 41 or battery unit, wherein, the active material of at least 60% is in conductive fiber material.

45. lead-acid batteries according to any one in claim 39 to 44 or battery unit, wherein, be no more than the active material of 80% in conductive fiber material.

46. lead-acid batteries according to any one in claim 1 to 41 or battery unit, wherein, by to be injected into comprising in electrode based on the paste of the particle of Pb and to make formation electric current by electrode, form the conductive chain of the particle based on Pb being attached to conductive fiber material.

47. lead-acid battery according to claim 46 or battery units, wherein, the particle based on Pb mainly comprises Pb and PbO particle.

48. lead-acid battery according to claim 47 or battery units, wherein, paste also comprises dilute sulfuric acid.

49. lead-acid battery according to claim 48 or battery units, wherein, the paste in injecting electrode also comprises dilute sulfuric acid, and described dilute sulfuric acid comprises by weight 0% and sulfuric acid about between 5%.

50. lead-acid battery according to claim 48 or battery units, wherein, the paste in injecting electrode also comprises dilute sulfuric acid, and described dilute sulfuric acid comprises by weight 0% and sulfuric acid about between 3%.

51. lead-acid battery according to claim 48 or battery units, wherein, the paste in injecting electrode also comprises dilute sulfuric acid, and described dilute sulfuric acid comprises weighing scale by paste 0% and sulfuric acid about between 5%.

52. lead-acid batteries according to any one in claim 46 to 51 or battery unit, wherein, the average particle size of the particle based on Pb of paste during injection is less than 10 microns.

53. lead-acid batteries according to any one in claim 46 to 52 or battery unit, wherein, the paste be injected in electrode has enough low viscosity so that can flow on a horizontal surface under gravity (and and non-self supporting).

54. lead-acid batteries according to any one in claim 46 to 53 or battery unit, wherein, mix to be formed the step of paste by vibrating paste to assist in mixed process.

55. lead-acid batteries according to any one in claim 46 to 54 or battery unit, wherein, paste is injected into electrode and assists by putting on paste or electrode material or both vibrations being less than 2kHz.

56. lead-acid batteries according to any one in claim 46 to 54 or battery unit, wherein, paste is injected into electrode and assists by putting on paste or electrode material or both vibrations in 25 scopes to 500Hz.

57. lead-acid batteries according to any one in claim 46 to 56 or battery unit, wherein, paste also comprises swelling agent.

58. lead-acid battery according to claim 57 or battery units, wherein, swelling agent comprises lignosulfonate.

59. lead-acid batteries according to claim 57 or claim 58 or battery unit, wherein, swelling agent presses the weighing scale of paste between about 0.05% to 0.25% when injecting.

60. lead-acid batteries according to claim 57 or claim 58 or battery unit, wherein, swelling agent comprises claim 48, and wherein, swelling agent presses the weighing scale of paste between about 0.09% to 0.2% when injecting.

61. lead-acid batteries according to claim 57 or claim 58 or battery unit, wherein, swelling agent comprises claim 48, and wherein, swelling agent presses the weighing scale of paste between about 0.09% to 0.17% when injecting.

62. lead-acid batteries according to any one in claim 46 to 61 or battery unit, wherein, paste also comprises Ag, Bi, Zn or compound any in them, as anti-gasifying reagents.

63. lead-acid batteries according to any one in claim 1 to 62 or battery unit, wherein, electrode comprises the metal claw connected for outside along at least one edge.

64. lead-acid batteries according to any one in claim 1 to 62 or battery unit, wherein, electrode comprises the grand scale metal conductor being attached to conductive fiber material and pawl conductively in the one or both sides of conductive fiber material.

65. lead-acid battery according to claim 64 or battery units, wherein, grand scale metal conductor comprises metal wire or metal tape or grid.

66. lead-acid batteries according to claim 64 or 65 or battery unit, wherein, grand scale metal conductor comprises the metal line or belt of curved shape in the one or both sides of carbon fibre material.

67. lead-acid batteries according to claim 64 or 65 or battery unit, wherein, electrode comprises two-layer conductive fiber material, has metal line or belt between which.

68. lead-acid batteries according to any one in claim 1 to 67 or battery unit, wherein, 1/50 or less of any the inside dimension that the thickness of electrode (being transverse to the length of electrode and width or face inside dimension) is electrode.

69. lead-acid batteries according to any one in claim 1 to 67 or battery unit, wherein, 1/100 or less of any the inside dimension that the thickness of electrode (being transverse to the length of electrode and width or face inside dimension) is electrode.

70. lead-acid batteries according to any one in claim 1 to 69 or battery unit, wherein, electrode has the thickness (being transverse to the length of electrode and width or face inside dimension) being less than 5mm.

71. lead-acid batteries according to any one in claim 1 to 69 or battery unit, wherein, electrode has the thickness (being transverse to the length of electrode and width or face inside dimension) being less than 3mm.

72. lead-acid batteries according to any one in claim 1 to 71 or battery unit, wherein, described electrode is plane substantially, and the length had within the scope of 50 to 500mm and/or width.

73. lead-acid batteries according to any one in claim 1 to 71 or battery unit, wherein, described electrode is plane substantially, and the length had within the scope of 50 to 200mm and/or width.

74. lead-acid batteries according to any one in claim 1 to 73 or battery unit, wherein, electrode is plane substantially, and has along the metal claw connected for outside at least one edge of electrode the size being less than 100mm.

75. lead-acid batteries according to any one in claim 1 to 73 or battery unit, wherein, electrode is plane substantially, and has along the metal claw connected for outside at least one edge of electrode the size being less than 70mm.

76. lead-acid batteries according to any one in claim 1 to 75 or battery unit, wherein, at least one electrode described is the negative pole of battery unit or battery.

77. lead-acid batteries according to any one in claim 1 to 75 or battery unit, wherein, at least one electrode described comprises whole negative poles of battery.

78. lead-acid batteries according to any one in claim 1 to 75 or battery unit, wherein, at least one electrode described is the positive pole of battery unit or battery.

79. lead-acid batteries according to any one in claim 1 to 75 or battery unit, wherein, at least one electrode described comprises whole positive poles of battery.

80. lead-acid batteries according to any one in claim 1 to 75 or battery unit, wherein, at least one electrode described is positive pole and the negative pole of battery unit or battery.

81. lead-acid batteries according to any one in claim 1 to 75 or battery unit, wherein, at least one electrode described comprises whole positive poles and the negative pole of battery.

82. 1 kinds of lead-acid batteries or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and comprises metal grate, described electrode also comprises and generates the electrolyte active material of electric current, described active material at least 20% in conductive fiber material.

83. lead-acid batteries according to Claim 8 described in 2 or battery unit, wherein, at least 20% but the active material being no more than 80% in conductive fiber material.

84. according to Claim 82 or lead-acid battery described in claim 83 or battery unit, wherein, conductive fiber material comprises individual layer in the side of metal grate.

85. according to Claim 82 or lead-acid battery described in claim 83 or battery unit, wherein, at least side of conductive fiber material in the both sides of metal grate comprises multiple layer.

86. 1 kinds of lead-acid batteries or battery unit, comprise at least one electrode, described electrode comprises conductive fiber material as collector, and comprises metal grate, described electrode also comprises electric current and generates electrolyte active material, and conductive fiber material has the volume resistivity being less than 10 Ω mm.

87. 1 kinds of lead-acid batteries or battery unit, wherein, the particle based on Pb and the weighing scale by the paste paste at the swelling agent about between 0.09% and 0.15% is comprised by injecting, and make formation electric current by electrode, form the conductive chain of the particle based on Pb being attached to conductive fiber material.

88. lead-acid batteries according to Claim 8 described in 7 or battery unit, wherein, described swelling agent comprises lignosulfonate.

89. lead-acid batteries according to Claim 8 described in 7 or battery unit, wherein, the particle based on Pb mainly comprises Pb and PbO particle.

Lead-acid battery described in 90. any one according to Claim 8 in 7 to 89 or battery unit, wherein, described paste also comprises dilute sulfuric acid.

Lead-acid battery described in 91. any one according to Claim 8 in 7 to 89 or battery unit, wherein, when being injected into electrode, paste also comprises dilute sulfuric acid, and described dilute sulfuric acid is included in 0 and sulfuric acid about between 2.5% by the weighing scale of paste.

Lead-acid battery described in 92. any one according to Claim 8 in 7 to 89 or battery unit, wherein, when being injected into electrode, paste comprises weighing scale by paste 0 and sulfuric acid about between 2%.

93. lead-acid batteries according to any one in claim 1 to 92 or battery unit, use Axion DCA test, 10, in 000 cycle, keeps the average DCA of at least 0.6A/Ah of per charging stage.

94. lead-acid batteries according to any one in claim 1 to 92 or battery unit, use Axion DCA test, 10, in 000 cycle, keeps the average DCA of at least 0.7A/Ah of per charging stage.

95. lead-acid batteries according to any one in claim 1 to 92 or battery unit, use Axion DCA test, 10, in 000 cycle, keeps the average DCA of at least 0.8A/Ah of per charging stage.

96. lead-acid batteries according to any one in claim 1 to 85 or battery unit, after 5000 cycles, keep the DCA of the initial DCA of at least 70% (when first time is full of electricity).

97. lead-acid batteries according to any one in claim 1 to 85 or battery unit, after 5000 cycles, keep the DCA of the initial DCA of at least 80% (when first time is full of electricity).

98. lead-acid batteries according to any one in claim 1 to 85 or battery unit, after 10000 cycles, keep the DCA of the initial DCA of at least 70% (when first time is full of electricity).

99. lead-acid batteries according to any one in claim 1 to 85 or battery unit, after 10000 cycles, keep the DCA of the initial DCA of at least 80% or 90% (when first time is full of electricity).

100. lead-acid batteries according to any one in claim 1 to 89 or battery unit, have the CCA grade of (electrode zone in the face of another electrode) at least 100mA/ square centimeter.

101. lead-acid batteries according to any one in claim 1 to 89 or battery unit, have the CCA grade of (electrode zone in the face of another electrode) at least 200mA/ square centimeter.

102. lead-acid batteries according to any one in claim 1 to 89 or battery unit, have the CCA grade of (electrode zone in the face of another electrode) at least 250mA/ square centimeter.

103. lead-acid batteries according to any one in claim 1 to 91 or battery unit, have the utilance of at least 55%.

104. lead-acid batteries according to any one in claim 1 to 91 or battery unit, have the utilance of at least 60%.

105. lead-acid batteries according to any one in claim 1 to 91 or battery unit, have the utilance of at least 70%.

106. lead-acid batteries according to any one in claim 1 to 91 or battery unit, have the utilance of at least 80%.

107. one kinds of hybrid vehicles, comprise the battery according to any one in claim 1 to 106.

108. according to the hybrid vehicle described in claim 107, has stopping-start-up performance.

109., according to the hybrid vehicle described in claim 107, have regenerative braking capability.

110. hybrid vehicles according to any one in claim 107-109, wherein, battery carries assistant load when it is shut off.

112. one kinds of methods for the manufacture of lead-acid battery or battery unit, the method comprises: form at least one (non-synthetic or synthesis) electrode to comprise conductive fiber material as collector, described conductive fiber material has the voidage (being the volume fraction that the hole between lead and conductive fiber occupies) when being full of electricity at least about 0.3, and the lead (in any form) when being converted to volume ratio in the scope of 0.7:1 to about 15:1 is loaded into than (respectively at least major part of electrode) with the quality of the quality of conductive fiber.

113. one kinds of methods for the manufacture of lead-acid battery or battery unit, the method comprises: form at least one (non-synthetic or synthesis) electrode to comprise conductive fiber material as collector, conductive fiber material has the voidage (being the volume fraction that the hole between lead and conductive fiber occupies) when being full of electricity at least about 0.3, and the lead when being converted to volume ratio in the scope of about 1:1 to about 10:1 is loaded into ratio with the quality of the quality of conductive fiber.

114. one kinds of methods for the manufacture of lead-acid battery or battery unit, the method comprises: form at least one (non-synthetic or synthesis) electrode to comprise conductive fiber material as collector, conductive fiber material has the voidage (being the volume fraction that the hole between lead and conductive fiber occupies) when being full of electricity, and the lead (in any form) when being converted to volume ratio is loaded into than (respectively at least major part of electrode) with the quality of the quality of conductive fiber, they to be loaded into and the quality of the quality of conductive fiber plumbous when being converted to volume ratio in voidage (x-axis) together and the figure than (y-axis) define a bit, this point drop on by described figure with in the region defined with slope about-1/0.3 another line from the x-axis space angle value of about 70% on the line of slope about-1/0.02 from the x-axis space angle value of about 98% and described figure.